Cationic alcohols and uses thereof

ABSTRACT

Compositions are disclosed comprising novel fluorinated cationic alcohols in a cosmetically acceptable vehicle. The fluorinated compounds alter a surface property of the hair to provide hair conditioning, for example. In embodiments, the compounds have improved water solubility and deposition properties.

This application is a divisional of U.S. application Ser. No.13/547,522, filed Jul. 12, 2012, which is a continuation of U.S.application Ser. No. 12/883,762, filed Sep. 16, 2010, now U.S. Pat. No.8,242,309, which claims the benefit of U.S. Provisional Application No.61/243,066, filed Sep. 16, 2009 and U.S. Provisional Application No.61/320,362, filed Apr. 2, 2010, all of which are incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention is directed to cationic fluorinated alcohols, compositionscontaining the same, and methods for treating surfaces such as hair andskin.

2. Description of Related Art

Hair conditioning refers to the process of imparting attributes such assmoothness, softness, and ease of styling to hair. Conditioning may alsoreduce a feeling of dryness and impart shine. Both damaged and normalhair require conditioning, however, there is a greater need ofconditioning for damaged hair due to the negative attributes it imparts.There is no single sensory attribute that equates with the perception ofdamage, rather it is associated with a combination of tactile and visualproperties. For example, damaged hair in general is more hydrophilicleaving it susceptible to moisture flux which increases its propensityfor swelling and breakage leading to a rough texture. Additionally,damaged hair tends to have a duller appearance due to the scattering oflight from its rough, non-uniform surface. Hair damage may be caused byenvironmental factors, such as chemical attack from bleaches, dyes andpollutants, photodamage from the sun, heat damage from a dryer or flatiron, or mechanical damage from styling. However, a perception of damagemay also arise when hair has not been subject to these environmentalfactors, but from the hair being coarse or varied in lipid content andspecific lipid composition. Improving upon benefits such ashydrophobicity, shine and tactile properties leads to the perception ofhealthier, more conditioned hair.

Among the best known hair conditioners are long chain quaternaryammonium compounds and fatty alcohols which have been used extensivelyin the prior art. The positively charged ammonium moiety of long chainquaternary ammonium compounds is attracted to the negatively chargedsurfaces of the keratin fibers, while the long chain portions of thesemolecules form a coating on the hair to create a perception ofsmoothness and increase the manageability of the hair.

Silicones are also widely used in hair conditioner products. Theseproducts likewise form a coating on the hair shaft, and may be providedwith an amino functionality or other chemical functionality to impartcharge. Silicones are frequently copolymerized and co-formulated withother polymers to provide a product having a combination of attributes.

The principle sensory drawback associated with all of the prior artconditioners is that the hair tends to feel coated and heavy, drivingthe consumer to wash and re-style their hair more frequently, leading tofurther damage. In addition to silicones, the oleophilic portions offatty alcohols and higher molecular weight quatenary compounds may causehair to feel oily. Additionally, the majority of compounds used toprovide shine properties to hair are typically oils and silicones,leading to a somewhat undesirable tactile perception over time.

Thus, there is an unmet need in the art for robust conditioningcompositions that can be used to condition hair that is perceived asbeing damaged, without the sensory drawbacks associated with the priorart compositions.

Cationic molecules have been used extensively for various applicationsincluding hair and skin conditioning, surface modification, as wettingagents, and industrial surfactants. Fluorinated compounds have also beenused in cosmetic formulations. For example, GB Application No. 1 598 567discloses fluorinated surfactants such as Zonyl® used in combinationwith silicones in a hair conditioner in an effort to render theconditioner more grease resistant, i.e., less oily.

U.S. Pat. Nos. 7,763,240 and 7,785,575 (which are assigned to theassignee herein) describe fluorinated compounds useful in hair careproducts to control moisture penetration into the hair (frizz control).Compositions containing these compounds resist dirt, avoid a feeling ofgreasiness or oiliness in the hair and leave a low amount of residue(i.e., are “weightless”).

It has now been discovered that certain cationic fluorinated alcohols,which can be synthesized by the reaction of a fluorinated epoxide and atertiary amine, have novel and beneficial effects when applied to hair.These compounds have improved deposition properties, so that they impartan improved feel to damaged, dry and coarse hair, without the sensorydrawbacks associated with the prior art. More specifically, certaininventive compounds described herein have demonstrated significantdeposit from rinse out formulations, leading to positive attributes suchas increasing the contact angle of damaged hair, imparting shine whichlasts through shampoo cycles, and reducing friction on damaged ends.

In embodiments, the compounds and compositions described herein arecapable of modifying or treating surfaces including skin, hair, fabrics,solids, and may be employed as surfactants and/or surface modifyingagents for improving chemical reactions.

SUMMARY OF THE INVENTION

In one aspect, the invention is a class of novel fluorinated cationicalcohols according to the following formula (I), including cosmeticallyacceptable salts thereof:

wherein, X¹ is O or —(CH₂)_(m)— (m being an integer between 1 and 20);R¹¹, R¹² and R¹³ are independently C₁₋₆ alkyl or C₁₋₆ hydroxyalkyl; andn is an integer from 1 to 20. These compounds are non-perfluorinated,preferably having a terminal CHF₂ group, and thus may be readilydistinguished from the perfluorinated surfactants used in the prior artfor a variety of purposes.

Alternatively, X¹ is the residue of a hydroxy-reactive linker used inthe synthesis, such as a poly glycol (e.g., polypropylene glycol (PPG)or polyethylene glycol (PEG)). In the case of PEG used as a startingmaterial, X¹ is —(CH₂—CH₂—O)_(p)— (wherein p is an integer from 1 to10,000, depending on the molecular weight of the PEG starting material).In such embodiment, the definitions of the other groups are the same asin the preceding paragraph.

In embodiments, the compound according to formula (I) has the followingstructure:

including cosmetically acceptable salts thereof, wherein n is an integerfrom 1 to 20.

In another aspect the invention is a compound according to Formula (III)comprising two or more linked quaternary moieties.

including cosmetically acceptable salts.

In Formula (III), A′ and A″ are independently CH₂, CHF or CF₂; X′ and X″are independently O, CF₂, or —(CH₂)_(m)—; Y′ and Y″ are independentlyCH₂, CHF or CF₂; R⁵ and R¹⁰ are the same or different organic groups,each substituted with at least two fluorine atoms; R⁶ and R⁹ areindependently substituted or unsubstituted C₁₋₆ alkyl, and may join toform a ring; R⁷ and R⁸ are independently substituted or unsubstitutedC₁₋₆ alkyl, and may join to form a ring; n is an integer from 1 to 20;and m is an integer from 1 to 20. Q is a divalent alkyl, alkenyl,alkynyl, alkoxy, cycloalkyl, aryl, alkoxy; acyl; acyloxy;heterocycloalkyl, hydroxyalkyl, thioalkyl; aliphatic; heteroaliphatic;cycloaryl; or heteroaryl group; any of which may be substituted orunsubstituted, linear or branched. For example, Q may be —(CH₂)_(t)—;—CH₂CH₂O)t-; —(CH₂CH(CH₃)—O)t-; —(CH₂CH(OH)—CH₂)t-; —(CH₂C(═O))t-;—(CH₂S—CH₂)t- (wherein t is an integer from 1 to 10,000).

In embodiments, the compound according to Formula (III) is notperfluorinated. For example, R⁵ and R¹⁰ may be identical straight orbranched chain C₁₋₃₀ fluoroalkyl groups having a terminal CHF₂ group.

In embodiments, the compound according to Formula (III) comprises twoidentical quaternary moieties linked by an alkylene group, so that A′and A″ are the same, X′ and X″ are the same, Y′ and Y″ are the same, R⁵and R¹⁰ are the same; R⁶ is the same as R⁸; and R⁷ is the same as R⁹.

In other embodiments, the compound according to Formula (III), isprovided with one or more additional cationic quaternary moieties, sothat one or more of R⁶, R⁷, R⁸, and R⁹ is defined by the followingformula:

wherein, X is O, CF₂, or —(CH₂)_(q)—; A is CH₂, CFH or CF₂; Y is CH₂,CFH or CF₂; R^(2′) and R^(3′) are independently hydrogen; aliphatic;heteroaliphatic; acyl; aryl; or heteroaryl; any of which may besubstituted or unsubstituted; or any of R^(2′), and R^(3′) may join toform a ring with a quaternary nitrogen; p is an integer from 1 to 20;and q is an integer from 1 to 20.

In another aspect, the compound according to Formula (III) takes theform of Formula (III′) in which the quaternary moieties are linked by analkylene group:

including cosmetically acceptable salts.

In Formula (III′), A′ and A″ are independently CH₂, CHF or CF₂; X′ andX″ are independently O, CF₂, or —(CH₂)_(m)—; R⁵ and R¹⁰ are the same ordifferent organic groups, each substituted with at least two fluorineatoms; R⁶ and R⁹ are independently substituted or unsubstituted C₁₋₆alkyl, and may join to form a ring; R⁷ and R⁸ are independentlysubstituted or unsubstituted C₁₋₆ alkyl, and may join to form a ring; nis an integer from 1 to 20; and m is an integer from 1 to 20.

In embodiments, the compound according to Formula (III′) is notperfluorinated. For example, R⁵ and R¹⁰ may be identical straight orbranched chain C₁₋₃₀ fluoroalkyl groups having a terminal CHF₂ group.

In embodiments, the compound according to Formula (III′) comprises twoidentical quaternary moieties linked by an alkylene group, so that A′and A″ are the same, X′ and X″ are the same, R⁵ and R¹⁰ are the same; R⁶is the same as R⁸, and R⁷ is the same as R⁹.

In other embodiments, the compound according to Formula (III′), isprovided with one or more additional cationic quaternary moieties, sothat one or more of R⁶, R⁷, R⁸, and R⁹ is defined by the followingformula:

wherein, X is O, CF₂, or —(CH₂)_(q)—; A is CH₂, CFH or CF₂; R^(2′) andR^(3′) are independently hydrogen; aliphatic; heteroaliphatic; acyl;aryl; or heteroaryl; any of which may be substituted or unsubstituted;or any of R^(2′), and R^(3′) may join to form a ring with a quaternarynitrogen; p is an integer from 1 to 20; and q is an integer from 1 to20.

In still another aspect, the invention is a composition for treatingskin or hair, comprising a cosmetically acceptable excipient, and acompound of formula (III) or (III′), as described above, or acosmetically acceptable salt thereof.

In still another aspect, the invention is a method for treating haircomprising applying to hair a composition comprising the compoundaccording to Formula (III) or (III′), in an amount effective to alter asurface property of the hair.

In another aspect, the invention is a composition for treating skin orhair, comprising a cosmetically acceptable excipient and a compound offormula (IV) including cosmetically acceptable salts thereof

In Formula (IV), X is O, CF₂, or —(CH₂)_(m)— (wherein m is 1 to 20); Ais CH₂, CHF or CF₂; R¹ is an organic group substituted with at least twofluorine atoms; R², R³, and R⁴ are independently aliphatic;heteroaliphatic; alkoxy; acyl; aryl; or heteroaryl; any of which may besubstituted or unsubstituted; and any of R², R³, and R⁴ may join to formone or more rings. In embodiments, one or more of R², R³, and R⁴contains at least one fluoro substituent. These fluorinated alcoholshave not previously been used in a hair conditioning composition.Compositions for treating hair containing perfluorinated compoundsaccording to Formula (IV) are within the scope of the invention, butnon-perfluorinated compounds are presently preferred. For example, R¹may be a C₁₋₃₀ straight or branched chain fluoroalkyl group with aterminal CHF₂ group.

In an alternative embodiment, X in formula (I) is the residue of ahydroxy-reactive linker used in the synthesis, including withoutlimitation, a poly glycol (e.g., polypropylene glycol (PPG) orpolyethylene glycol (PEG)). In the case of PEG used as a startingmaterial, for example, X may be —(CH₂—CH₂—O)_(p)— (wherein p is aninteger from 1 to 10,000, depending on the molecular weight of the PEGstarting material). In such embodiment, the definitions of A, R¹, R²,R³, and R⁴ are the same as for the embodiment described in the precedingparagraph.

In another aspect, the invention is a corresponding method of treatinghair, comprising applying to hair a composition comprising a compound offormula (IV), as defined above.

In another aspect, the invention is a cosmetic composition for treatinghair or skin comprising the reaction product of a fluorinated epoxideand a tertiary amine and a cosmetically acceptable excipient, saidreaction product comprising a quaternary ammonium moiety, a hydroxylgroup, and containing at least two fluorine atoms. In embodiments thetertiary amine is a diamine. In embodiments the fluorinated epoxide isnot perfluorinated.

In still another aspect, the invention is a method of treating haircomprising applying a cosmetic composition comprising the reactionproduct of a fluorinated epoxide and a tertiary amine.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the results of a feel test comparison in which threeprinciple feel parameters were assessed on hair treated with a shampooand conditioner (Formulation Examples 2 and 3 respectively) according tothe invention, hair treated with a leading prior art conditioningshampoo, and a control.

FIG. 2 depicts the results of the comparison of FIG. 1, with theparameters totaled.

FIG. 3 depicts the results of a feel test comparison, similar to thetest conducted in FIG. 1, except that the test is conducted on moreseverely damaged hair.

FIG. 4 depicts the results of the comparison of FIG. 3, with theparameters totaled.

FIG. 5 depicts the results of a feel test comparison, similar to FIG. 1,except conducted on the most severely damaged hair.

FIG. 6 depicts the results of the comparison of FIG. 5, with theparameters totaled.

FIG. 7 graphically shows an improvement in feel test comparison scoresfor a composition according to the invention for increasing levels ofdamage.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Definitions

Definitions of specific functional groups and chemical terms aredescribed in more detail below. For purposes of this invention, thechemical elements are identified in accordance with the Periodic Tableof the Elements, CAS version, Handbook of Chemistry and Physics, 75^(th)Ed., and specific functional groups are generally defined as describedtherein. Additionally, general principles of organic chemistry, as wellas specific functional moieties and reactivity, are described in OrganicChemistry, Thomas Sorrell, University Science Books, Sausalito (1999),the entire contents of which are incorporated herein by reference.

Unless expressly stated otherwise, the compounds and groups describedherein may be substituted with any number of substituents or functionalmoieties permitted by the valences of the respective compound or group.In general, the term “substituted” whether preceded by the term“optionally” or not, and substituents contained in formulas of thisinvention, refer to the replacement of hydrogen atoms in a givenstructure with a specified substituent. Unless stated otherwise, whenmore than one position in any given structure may be substituted withmore than one substituent selected from a specified group, thesubstituent may be either the same or different at every position. Asused herein, the term “substituted” is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and non-aromaticsubstituents of organic compounds. For purposes of this invention,heteroatoms such as nitrogen, oxygen or sulfur, may be bonded tohydrogen atoms or be substituted with any permissible substituents oforganic compounds described herein which satisfy the valencies of theheteroatoms.

Where a carbon atom in a chain may be replaced with a heteroatom, thisis also sometimes referred to as a “substitution.”

The term acyl as used herein refers to a group having the generalformula —C(O)R, where R is alkyl, alkenyl, alkynyl, aryl, carbocylic,heterocyclic, or aromatic heterocyclic. An example of an acyl group isacetyl. The term acyloxy refers to the group —OC(O)R, which forms anester when bonded to another chemical group.

The term aliphatic, as used herein, refers to a saturated orunsaturated, straight chain (i.e., unbranched), branched, acyclic,cyclic, or polycyclic hydrocarbon backbone, which is optionallysubstituted with one or more functional groups. As will be appreciatedby one of ordinary skill in the art, “aliphatic” is intended herein toinclude, but is not limited to, alkyl, alkenyl, alkynyl, cycloalkyl,cycloalkenyl, and cycloalkynyl moieties.

The term alkyl as used herein refers to a saturated, straight- orbranched-chain hydrocarbon group derived from a hydrocarbon containingbetween one and thirty carbon atoms by removal of a single hydrogenatom. In some embodiments, the alkyl group contains 1-10 carbon atoms.In another embodiment, the alkyl group contains 1-8 carbon atoms. Instill other embodiments, the alkyl group contains 1-6 carbon atoms. Inyet another embodiment, the alkyl group contains 1-4 carbons. Examplesof alkyl groups include, but are not limited to, methyl, ethyl,n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, sec-pentyl,iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl,n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like, which maybear one or more substituents. As used herein, the term “alkyl” includesstraight, branched and cyclic alkyl groups. An analogous conventionapplies to other generic terms such as “alkenyl”, “alkynyl”, and thelike. Furthermore, as used herein, the terms “alkyl”, “alkenyl”,“alkynyl,” and the like, encompass both substituted and unsubstitutedgroups. In certain embodiments, as used herein, “lower alkyl” is used toindicate those alkyl groups (cyclic, acyclic, substituted,unsubstituted, branched or unbranched) having 1-6 carbon atoms.

The term alkoxy as used herein refers to a saturated (i.e., alkyl-O—) orunsaturated (i.e., alkenyl-O— and alkynyl-O—) group attached to theparent molecular moiety through an oxygen atom. In certain embodiments,the alkyl, alkenyl or alkynyl group contains 1-20 aliphatic carbonatoms. In certain other embodiments, the alkyl, alkenyl, and alkynylgroups employed in the alkoxy groups of the invention contain 1-8aliphatic carbon atoms. In still other embodiments, the alkyl groupcontains 1-6 aliphatic carbon atoms. In yet other embodiments, the alkylgroup contains 1-4 aliphatic carbon atoms. Examples include, but are notlimited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy,i-butoxy, sec-butoxy, neopentoxy, n-hexoxy, and the like.

The term alkenyl denotes a monovalent group derived from a hydrocarbonmoiety having at least one carbon-carbon double bond by the removal of asingle hydrogen atom. In certain embodiments, the alkenyl group employedin the invention contains 1-20 carbon atoms. In some embodiments, thealkenyl group employed in the invention contains 1-10 carbon atoms. Inanother embodiment, the alkenyl group employed contains 1-8 carbonatoms. In still other embodiments, the alkenyl group contains 1-6 carbonatoms. In yet another embodiments, the alkenyl group contains 1-4carbons. Alkenyl groups include, for example, ethenyl, propenyl,butenyl, 1-methyl-2-buten-1-yl, and the like.

The term alkynyl as used herein refers to a monovalent group derivedfrom a hydrocarbon having at least one carbon-carbon triple bond by theremoval of a single hydrogen atom. In certain embodiments, the alkynylgroup employed in the invention contains 1-20 carbon atoms. In someembodiments, the alkynyl group employed in the invention contains 1-10carbon atoms. In another embodiment, the alkynyl group employed contains1-8 carbon atoms. In still other embodiments, the alkynyl group contains1-6 carbon atoms. Representative alkynyl groups include, but are notlimited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.

The term alkylamino refers to a group having the structure —NHR′ whereinR′ is an alkyl group, as previously defined (examples includemethylamino and ethylamino); and the term dialkylamino refers to a grouphaving the structure —NR′R″, wherein R′ and R″ are each independentlyselected from the group consisting of alkyl groups (examples includedimethylamino, diethylamino and methylethylamino). The termtrialkylamino refers to a group having the structure —NR′R″R′″, whereinR′, R″, and R′″ are each independently selected from the groupconsisting of alkyl groups. In certain embodiments, the alkyl groupcontain 1-20 aliphatic carbon atoms. In certain other embodiments, thealkyl group contains 1-10 aliphatic carbon atoms. In yet otherembodiments, the alkyl group contains 1-8 aliphatic carbon atoms. Instill other embodiments, the alkyl group contain 1-6 aliphatic carbonatoms. In yet other embodiments, the alkyl group contain 1-4 aliphaticcarbon atoms. Additionally, R′, R″, and/or R′″ taken together mayoptionally be —(CH₂)_(k)— where k is an integer from 2 to 6, to form aring (piperidino is an example).

An amino group, as used herein, encompasses alkylamino, dialkylamino andtrialkylamino groups (as defined above), and aminoalkyl likewiseincludes —RNH₂, —RNHR′, —RNR′R″ and —RNR′R″R′″. A tertiary amine as usedherein is an organic compound in which all three hydrogens of ammoniaare replaced with organic groups. A tertiary amine may include adiamine, in which two amino groups are linked.

The term aromatic, as used herein, refers to a moiety having delocalizedelectrons due to conjugated double bonds, which may form a ring (as inan aryl moiety); heteroaromatic means an aromatic compound in which atleast one of the atoms in the ring or aromatic chain is a nitrogen,oxygen, phosphorus, silicon or sulfur atom.

In general, the terms aryl and heteroaryl, as used herein, refer tomono- or polycyclic, heterocyclic, polycyclic, and polyheterocyclicunsaturated moieties having preferably 3-14 carbon atoms, each of whichmay be substituted or unsubstituted. Substituents include, but are notlimited to, any of the previously mentioned substituents, i.e., thesubstituents recited for aliphatic moieties, or for other moieties asdisclosed herein, resulting in the formation of a stable compound. Incertain embodiments of the present invention, aryl refers to a mono- orbicyclic carbocyclic ring system having one or two aromatic ringsincluding, but not limited to, phenyl, naphthyl, tetrahydronaphthyl,indanyl, indenyl, and the like. In certain embodiments of the presentinvention, the term heteroaryl, as used herein, refers to a cyclicaromatic group having from five to ten ring atoms of which one ring atomis selected from S, O, and N; zero, one, or two ring atoms areadditional heteroatoms independently selected from S, O, and N; and theremaining ring atoms are carbon, the group being joined to the rest ofthe molecule via any of the ring atoms, such as, for example, pyridyl,pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl,oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl,quinolinyl, isoquinolinyl, and the like.

It will be appreciated that aryl and heteroaryl groups can beunsubstituted or substituted, wherein substitution includes replacementof one, two, three, or more of the hydrogen atoms thereon independentlywith any one or more of the following moieties including, but notlimited to: aliphatic; heteroaliphatic; aryl; heteroaryl; arylalkyl;heteroarylalkyl; alkoxy; aryloxy; heteroalkoxy; heteroaryloxy;alkylthio; arylthio; heteroalkylthio; heteroarylthio; —F; —Cl; —Br; —I;—OH; —NO₂; —CN; —CF₃; —CH₂CF₃; —CHCl₂; —CH₂OH; —CH₂CH₂OH; —CH₂NH₂;—CH₂SO₂CH₃; —C(O)R_(x); —CO₂(R_(x)); —CON(R_(x))₂; —OC(O)R_(x);—OCO₂R_(x); —OCON(R_(x))₂; —N(R_(x))₂; —S(O)₂R_(x); —NR_(x)(CO)R_(x),wherein each occurrence of R_(x) independently includes, but is notlimited to, aliphatic, heteroaliphatic, aryl, heteroaryl, arylalkyl, orheteroarylalkyl, wherein any of the aliphatic, heteroaliphatic,arylalkyl, or heteroarylalkyl substituents described above and hereinmay be substituted or unsubstituted, branched or unbranched, cyclic oracyclic, and wherein any of the aryl or heteroaryl substituentsdescribed above and herein may be substituted or unsubstituted.Additional examples of generally applicable substituents are illustratedby the specific embodiments shown in the Examples that are describedherein.

A carboxyl group, as used herein, refers to the radical —CO₂H. Acarboxyl group is sometimes referred to herein as a hydroxycarbonylgroup. The term carboxylic acid as used herein refers to a compound witha terminal —CO₂H group.

The terms halo and halogen as used herein refer to an atom selected fromfluorine, chlorine, bromine, and iodine.

The term heteroaliphatic, as used herein, refers to an aliphatic moietyin which one or more carbon atoms in the backbone is replaced with anoxygen, sulfur, nitrogen, phosphorus, or silicon atom, i.e., in place ofcarbon atoms in the chain. Heteroaliphatic moieties may be branched,unbranched, cyclic or acyclic and include saturated and unsaturatedheterocycles such as morpholino, pyrrolidinyl, etc.

The term heterocyclic, as used herein, refers to an aromatic ornon-aromatic, partially unsaturated or fully saturated, 3- to10-membered ring system, which includes single rings of 3 to 8 atoms insize and bi- and tri-cyclic ring systems which may include aromaticfive- or six-membered aryl or aromatic heterocyclic groups fused to anon-aromatic ring. These heterocyclic rings include those having fromone to three heteroatoms independently selected from oxygen, sulfur, andnitrogen, in which the nitrogen and sulfur heteroatoms may optionally beoxidized and the nitrogen heteroatom may optionally be quaternized. Incertain embodiments, the term heterocylic refers to a non-aromatic 5-,6-, or 7-membered ring or a polycyclic group wherein at least one ringatom is a heteroatom selected from O, S, and N (wherein the nitrogen andsulfur heteroatoms may be optionally oxidized), including, but notlimited to, a bi- or tri-cyclic group, comprising fused six-memberedrings having between one and three heteroatoms independently selectedfrom the oxygen, sulfur, and nitrogen, wherein (i) each 5-membered ringhas 0 to 2 double bonds, each 6-membered ring has 0 to 2 double bonds,and each 7-membered ring has 0 to 3 double bonds, (ii) the nitrogen andsulfur heteroatoms may be optionally oxidized, (iii) the nitrogenheteroatom may optionally be quaternized, and (iv) any of the aboveheterocyclic rings may be fused to an aryl or heteroaryl ring.

The term aromatic heterocyclic, as used herein, refers to a cyclicaromatic group having from five to ten ring atoms of which one ring atomis selected from sulfur, oxygen, and nitrogen; zero, one, or two ringatoms are additional heteroatoms independently selected from sulfur,oxygen, and nitrogen; and the remaining ring atoms are carbon, the groupbeing joined to the rest of the molecule via any of the ring atoms, suchas, for example, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl,imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl,thiophenyl, furanyl, quinolinyl, isoquinolinyl, and the like. Aromaticheterocyclic groups can be unsubstituted or substituted withsubstituents selected from the group consisting of branched andunbranched alkyl, alkenyl, alkynyl, haloalkyl, alkoxy, thioalkoxy,amino, alkylamino, dialkylamino, trialkylamino, acylamino, cyano,hydroxy, halo, mercapto, nitro, carboxyaldehyde, carboxy,alkoxycarbonyl, and carboxamide.

The term carbonyldioxyl, as used herein, refers to a carbonate group ofthe formula —O—CO—OR.

The term carbamoyl, as used herein, refers to an amide group of theformula —CONH₂.

The term thiohydroxyl or thiol, as used herein, refers to a group of theformula —SH.

The term ureido, as used herein, refers to a group of the formula—NH—CO—NH₂

The following are more general terms used throughout the presentapplication:

As used herein, the singular forms “a”, “an”, and “the” include theplural reference unless the context clearly indicates otherwise. Thus,for example, a reference to “a monomer” includes a plurality of suchmonomers.

The term “keratin” as used herein refers any one of a class of fibrousstructural proteins found in hair, wool, and nails. Keratin proteinscontains a large quantity of cysteine residues.

The term organic group refers broadly to any carbon-containing group.

The term perfluorinated as used herein means a chemical group in whichall the hydrogen atoms are replaced with fluorine atoms.

The term polymer refers to a molecule having three or more repeatingmonomer units. A repeating unit is a unit bonded directly to a pluralityof like units to form a linear chain. Preferred compounds herein arenon-polymeric. However, in embodiments, portions of the compound used ina composition according to the invention may contain a polymericpolyethylene or polyethylene glycol chain or other polymeric moiety.

A surface property of hair as used herein is broadly construed to referto any change in the surface of the hair caused by applying acomposition according to the invention. This may refer to the surfaceenergy (which may be measured on a surface other than the hair itself,using contact angle measurements, for example, or other methodology);frictional attributes of the hair; resistance to moisture (measured byvapor sorption/desorption (DVS) tests, for example, or othermethodology), resistance to dirt (measured by a starch test, forexample). In preferred embodiments, a surface property pertains to hairconditioning, so that the property of interest is the smoothness,softness, ease of detangling, shine, or amelioration of frizz. Althoughthese attributes may be somewhat subjective, methodologies for testingthem (including the “feel test” described herein) are widely used in theart.

Synthesis

The compounds useful in the compositions and methods of the inventionmay be prepared by reacting a tertiary amine with a fluorinated epoxideaccording to the following general schemes:

R^(2′), R^(3′) and R^(4′) in the above reaction schemes may be the sameor different organic groups, which may be substituted or unsubstituted.For example, R^(2′), R^(3′) and R^(4′) may be C₁₋₆ alkyl groups, whichmay be substituted with hydroxyl, carboxy, alkoxy or acyloxy groups.

In the above reaction scheme, any tertiary amine may be used. Inembodiments R^(2′), R^(3′) and R^(4′) are the same or differentaliphatic, heteroaliphatic, alkoxy, aryl or heteroaryl, any of which maybe substituted or unsubstituted. In preferred embodiments, R^(2′),R^(3′) and R^(4′) are C₁₋₃₀ alkyl groups, which may be substituted withhydroxyl or hydroxycarbonyl groups. Diamines and cyclic amines may alsobe used. In embodiments R^(2′), R^(3′) and R^(4′) may be alsoindependently substituted with one or more fluorine atoms. R_(f) is afluorinated organic group, such as C₁₋₃₀ branched or straight chainfluorinated alkyl, which may be perfluorinated or non-perfluorinated;for example, R_(f) may comprise a CH₂CHF or CF₂ group adjacent theepoxide moiety in the reactant and adjacent the hydroxyl carbon in thereaction product.

In embodiments, the tertiary amine is a diamine, which may be reactedwith a fluorinated epoxide according to the following reaction schemes.Consistent with the reactions above, in which a tertiary amine is used,a fluorinated epoxide without an ether linkage could also be used (notshown).

In the above reaction scheme R^(4′), R^(5′), R^(6′) and R^(7′) are thesame or different organic groups, which may be substituted orunsubstituted. In embodiments, R^(4′), R^(5′), R^(6′) and R^(7′) areC₁₋₆ alkyl groups, which may be substituted with hydroxyl, carboxy,alkoxy or acyloxy. R_(f) is a fluorinated organic group, such as C₁₋₃₀branched or straight chain fluorinated alkyl, which may beperfluorinated or non-perfluorinated. The amine moieties of the diaminein the scheme above may be linked by a C₁₋₂₀ alkenyl group, so that o inthe first reaction scheme above is 1 to 20. Alternatively, anotherlinking group may be used, such as a divalent alkyl, alkenyl, alkynyl,alkoxy, cycloalkyl, aryl, acyl, acyloxy, heterocycloalkyl, hydroxyalkyl,thioalkyl; aliphatic; heteroaliphatic; cycloaryl; or heteroaryl group;any of which may be substituted or unsubstituted, linear or branched.For example, Q may be —(CH₂)_(t)—; —(CH₂CH₂O)t-; —(CH₂CH(CH₃)—O)t-;—(CH₂CH(OH)—CH₂)t-; —(CH₂C(═O))t-; —(CH₂S—CH₂)t- (wherein t is aninteger from 1 to 10,000).

In the above reaction schemes, any reactive fluoro epoxy compound may beused, provided that it contains at least two fluorine atoms. Thus, R_(f)may be, without limitation, a branched or straight chain fluorinatedaliphatic group, a straight or branched chain fluorinatedheteroaliphatic group, a fluorinated acyl group, a fluorinated aryl orfluorinated heteroaryl group. R_(f) may be R¹-A-, wherein A is CH₂, CFH,or CF₂, preferably CH₂, and R¹ is an organic group containing at leasttwo fluorine atoms. R_(f) may include —(CF₂)_(m)—, wherein m is aninteger from 1 to 20.

If a hydroxy-reactive terminated linker is used in the synthesis of Rf,such as functionalized PEG, PPG, or other polyglycol, Rf may include alinking moiety having a formula such as —(CH₂—CH₂—O)_(p)—, wherein p isan integers from 1 to 10000, depending on the molecular weight of thestarting material.

Thus, in embodiments, the invention is a hair treatment compositioncomprising the reaction product of a fluorinated epoxide and a tertiaryamine according to the reaction schemes described above. In preferredembodiments, the reaction product is the reaction product of afluorinated epoxide and a tertiary amine selected from the groupconsisting of: trimethylamine; triethylamine; triisopropylamine;tributylamine methyldiethylamine; triethanolamine; triisopropanolamine;N-ethyldiethanolamine; N,N-dimethylethanolamine;N,N-diethylethanolamine; 3-diethylaminopropanol;1,3-bis(dimethylamino)-2-propanol; 5-diethylamino-2-pentanol;1-diethylamino-2-propanol; 2-(diethylamino)-1,2-propandiol;2-(diisopropylamino)ethanol; 3-diisopropylamino-1,2-propandiol;1-dimethylamino-2-propanol; 3-dimethylamino-1-propanol;3-dimethylaminopropylamine; tris(3-aminopropyl)amine;N,N,N′,N′-tetramethylethylenediamine and triethylenediamine;1-(2-dimethylaminoethyl)-4-methylpiperazine;2,2′,2″,2′-ethylenedinitrilotetraethanol;N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine; andN,N,N′,N″,N″-pentamethyldiethylenetriamine.

The fluorinatedepoxides, glycidyl 2,2,3,3,4,4,5,5-octafluoropentyl etherand glycidyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9 hexadecafluorononyl ether,used in the examples herein, are commercially available fromSigma-Aldrich, Inc. (St. Louis, Mo.).2-(4,4,5,5-tetrafluoro-2-oxapentyl)oxirane) and3-(1,1,2,2-Tetrafluoroethoxy)-1,2-propenoxide were obtained fromSynquest Labs (Alachua, Fla.). Other fluorinated epoxides that can alsobe used include, 3-(1H,1H,9H-Perfluorononyloxy)-1,2-propenoxide.

Perfluorinated species which can be used in the invention include1,2-epoxyperfluoroethane, 1,2-epoxyperfluoropropane,1,2-epoxyperfluoroisobutane, 1,2-epoxyperfluorobutane,2,3-epoxyperfluorobutane, 2,3-epoxyperfluoro-2-methylbutane,2,3-epoxy-perfluoro-2,3-dimethylbutane, 1,2-epoxyperfluoropentane,2,3-epoxyperfluoropentane, 1,2-epoxyperfluoro-2-ethylbutane,1,2-epoxyperfluorooctane, 1,2-epoxyperfluoro-1-cyclohexylethane,1,2-epoxyperfluoro-1,2-dicyclohexylethane,1,2-epoxyperfluoro-2-cyclohexyl-2-methyl-propane,perfluoroepoxyethylbenzene, perfluoro-(p-epoxyethyl)-toluene,1,2-epoxyperfluoro-1,2-diphenylethane, 1H,1H-Heptafluorobutyl epoxide,4,5,5,6,6,6-Hexafluoro-2-(trifluoromethyl)butyl epoxide,nonafluorobutylepoxide, (2,2,2-Trifluoroethyl)oxirane,2-(Trifluoromethyl)oxirane, 2,2-Bis(trifluoromethyl)oxirane,3-(Nonafluoro-tert-butyl)propen-1,2-oxide,2-(2,2,3,3,3-Pentafluoropropoxymethyl)oxirane,3-(1H,1H,9H-Perfluorononyloxy)-1,2-propenoxide,2-(1H,1H-Nonafluoropentyl)oxirane, 2-(1H,1H-Perfluoroundecyl)oxirane,2-(1H,1H-Perfluoroheptyl)oxirane,3-(Perfluoro-3-methylbutyl)-1,2-propenoxide,3-(Perfluoro-5-methylhexyl)-1,2-propenoxide,3-(Perfluoro-7-methyloctyl)-1,2-propenoxide,3-(Perfluorooctyl)-1,2-epoxypropane,1,4-Bis(epoxypropyl)octafluorobutane, and so forth. The synthesis ofsome of these compounds is described in U.S. Pat. No. 3,622,601. Thenon-perfluorinated analogs of these compounds may also be used.

In embodiments, R_(f) in the reaction scheme above is a C₂₋₃₀fluoroalkyl group. In preferred embodiments, R_(f) is notperfluorinated. For example, R_(f) is a straight chain C₂₋₃₀ fluoroalkylgroup with a terminal CHF₂ group, as in many of the examples below.

Non-limiting examples of amine starting materials used according to theinvention include: trimethylamine, triethylamine, triisopropylamine,tributylamine and methyldiethylamine. Those having active hydrogensinclude triethanolamine, triisopropanolamine, N-ethyldiethanolamine,N,N-dimethylethanolamine, N,N-diethylethanolamine,3-diethylaminopropanol, 1,3-bis(dimethylamino)-2-propanol,5-diethylamino-2-pentanol, 1-diethylamino-2-propanol,2-(diethylamino)-1,2-propandiol, 2-(diisopropylamino)ethanol,3-diisopropylamino-1,2-propandiol, 1-dimethylamino-2-propanol,3-dimethylamino-1-propanol, 3-dimethylaminopropylamine andtris(3-aminopropyl)amine.

Depending on the structure of the amine starting material, a variety ofphysiochemical properties such as solubility, melting temperature,viscosity, charge density may be targeted and obtained. One such exampleis to alter the optical properties of the cationic fluorinated alcoholby selecting high or low refractive amines resulting in high shine orhigh color contrast respectively. However, in some cases the followingtertiary amines may be used: bis(2-hydroxyethyl)cocoamine,polyoxyethylene cocoamine, bis(2-hydroxy ethyl)soyamine, polyoxyethylenesoyamine, bis(2-hydroxyethyl)tallow amine, polyoxyethylene tallowamine,bis(2-hydroxyethyl)oleylamine, polyoxyethylene oleylamine,bis(2-hydroxyethyl)octadecylamine, polyoxyethylene octadecylamine,N,N-dimethyl-dodecylamine, N,N-dimethyl-tetradecylamine,N,N-dimethyl-hexadecylamine, N,N dimethyl-octadecylamine,N,N-dimethyl-cocoamine, N,N-dimethyl soya amine,N,N-dimethyl-tallowamine, N,N-dimethyl-oleylamine, andN-methyl-distearylamine.

Examples herein were variously prepared using triethylamine andtriethanolamine, obtained from Sigma-Aldrich (St. Louis, Mo.);N,N,N′,N′-tetramethylethylenediamine and triethylenediamine;1-(2-dimethylaminoethyl)-4-methylpiperazine, 2,2′,″,2″-ethylenedinitrilotetraethanol;N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine; andN,N,N′,N″,N″-pentamethyldiethylenetriamine, purchased from TCI America(Portland, Oreg.); and N,N′-dimethylpiperazine andhexamethylenetetramine, purchased from Acros Chemicals.

Additional information about the reaction to form cationic alcoholsaccording to the invention may be found in Zeno W. Wicks, et al.,Organic Coatings: Science and Technology, John Wiley (1999), p 278,incorporated by reference.

Synthetic Example 1

A cationic fluorinated alcohol according to the invention, (Example 1 inTable 1 below) was made according to the following reaction scheme:

To 1 equivalent (0.308 g, 3.042 mmol) of triethylamine in a 7 mlscintillation vial with stirbar, 1 equivalent (0.174 ml) of glacialacetic acid was added and mixed well. 0.28 ml of de-ionized water wasadded so that the amine was dissolved or well dispersed. 1.01equivalents (1.5 g, 3.073 mmol) of Glycidyl2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl ether were added andthe mixture was uniformly stirred at high speed at 95° C. Thefluorinated epoxide separated into a different layer. After about 4 to 6hours, the two layers became homogeneous indicating that the reactionwas near completion. The mixture was stirred continuously overnight(about 16 hours). At the end of the reaction, a uniform clear solutionwas obtained. The water was removed under vacuum and the viscous productwas re-dissolved 2-3 times in absolute ethanol to remove any remainingwater. The mixture was purified by repeated precipitation (about 3-5times) from diethyl ether with hexane. Once the last wash, hexane wasadded to the material to form a slurry. The excess hexane was decantedoff and the gel-like material is dried under vacuum overnight, to yielda beige wax. ¹H NMR was performed on a Varian Mercury 300 MHzspectrometer. Mass Spectrometry was conducted using a Thermo FinniganLCQdeca mass spectrometer. ¹H NMR δ (CD₃OD, 300 MHz): 1.31 (t, 3H,—CH₂CH₃), 1.92 (t, 3H, CH₃COO⁻), 3.49 (m, 8H, N⁺(CH₂)₄), 3.71 (t, 2H,—OCH₂CF₂—), 4.18 (m, 2H, —CH(OH)CH₂O—), 4.27 (m, 1H, —CH(OH)CH₂O—), 6.70(t, 1H, —CF₂CHF₂). (+)-ESIMS 590.18 [M⁺].

In an alternative synthesis, hydrochloric acid was used instead ofglacial acetic acid: 5.0 ml of water was added to 1.05 equivalent (1.48g, 10.754 mmol) of triethylamine hydrochloride in a 20 ml scintillationvial with stirbar to dissolve the salt completely and was mixed well. Aclear solution was obtained. 1.0 equivalent (5.0 g, 10.242 mmol) ofGlycidyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl ether(HDFE) was added. The HDFE separated into a different layer at thebottom of the vial. The mixture was uniformly stirred at high speed at95° C. After about 2 hours, the 2 layers became homogeneous and clearindicating that the reaction was near completion. The solution wascolorless to pale yellow. The mixture was left stirring overnight for atotal of about 16 hours. Acetone was added to the solution and the waterwas removed under vacuum. This step was repeated 3 times to ensure thatmost of the water was removed. The product was warmed and dissolved in aminimal volume of diethyl ether. Cold hexane was added dropwise and thevial was cooled in an ice bath. The solid precipitated from thesolution. The solvents were removed by decantation. This precipitationstep was repeated 3 times until a clear gel-like material was obtained.The product was dried under vacuum to yield a white wax.

The cationic compounds disclosed herein may be associated with anycounter ion to form cosmetically acceptable salts, and the depiction ofthe cationic compound is intended to include all such salts. Thesynthesis examples above, for example, demonstrate the formation ofacetate and chloride salts, but others are known to those of ordinaryskill in the art. A reference Lists of suitable cosmetically acceptablesalts are found in Remington Pharmaceutical Sciences, 17th ed., MackPublishing Company, Easton, Pa., 1985, p. 1418.

Synthetic Example 2

A cationic fluorinated alcohol according to Example 2 in Table 1 belowwas synthesized as follows: to 1 equivalent (0.392 g, 3.433 mmol) ofN,N′-Dimethylpiperazine in a 7 ml scintillation vial with stirbar, 1equivalent (0.393 ml) of glacial acetic acid was added and mixed well.0.4 ml of de-ionized water was added so that the amine was welldispersed. 2.02 equivalents (2.0 g, 6.941 mmol) of glycidyl2,2,3,3,4,4,5,5-octafluoropentyl ether was added and the mixture wasuniformly stirred at high speed at 95° C. After about 4 to 6 hours, thetwo layers become homogeneous indicating that the reaction was nearcompletion. The mixture was stirred continuously overnight (about 16hours). At the end of the reaction, a uniform clear solution wasobtained. The water was removed under vacuum and the viscous product wasre-dissolved 2-3 times in absolute ethanol to remove any remainingwater. The mixture was purified by repeated precipitation (about 3-5times) from diethyl ether with hexane. The excess hexane was decantedoff and the viscous material was dried under vacuum overnight. A paleyellow liquid was obtained. NMR confirmed the identify of the moleculeas the second entry in Table 1 below.

Synthetic Example 3

The cationic alcohol of Example 15 in Table 1 was prepared according tothe following reaction scheme:

An intermediate salt N,N,N′,N′-TetramethylethylenediamineDi-Hydrochloride (“TEMED-HCl”) was prepared as shown in step 1 byweighing 1 equivalent (20 g, 172.06 mmol) ofN,N,N′,N′-Tetramethylethylenediamine (TEMED; Aldrich, 99.5% purity) intoa 500 ml round bottom flask containing a magnetic stir bar. 20 g ofde-ionized water was added and the mixture was stirred at roomtemperature until a uniform clear solution was obtained. 2.09equivalents (36 g, 360 mmol) of 10N HCl was weighed into a graduateddropping funnel with a pressure equalizing arm. The round bottom flaskwas set up in an ice-bath and the dropping funnel was attached. The HClwas slowly added over about one hour with constant stirring in theice-bath. After complete addition, the reaction mixture was allowed toreact further for one hour. The resulting clear solution wasconcentrated under reduced pressure using a rotovap followed by repeatedco-evaporations with acetone to yield a white crystalline solid. Thesolid was washed a few times with hexane and cold diethyl ether toremove any impurities and dried under vacuum to yield 31 g (95%) of awhite crystalline solid. ¹H NMR (300 MHz, D₂O, 25° C.): δ 2.90 (t, 12H);3.65 (d, 4H).

To 1 equivalent (41.6 g, 222.3 mmol) of TEMED-HCl salt prepared in step1, 100 ml of water was added and mixed until a clear solution wasobtained. 2.2 equivalents (92.0 g, 489 mmol) of glycidyl2,2,3,3-tetrafluoropropyl ether was added dropwise using a droppingfunnel over a period of 2 hours. The mixture was uniformly stirred athigh speed at 95° C. and left stirring for a total of 16 h until a clearhomogeneous solution was obtained. The solution was then washed withdichloromethane three times and the aqueous solution was evaporated todryness under vacuum. The oily residue was then stripped from acetoneand evaporated to dryness. The final obtained waxy residue was dried ina vacuum oven at a temperature of 50° C. overnight to give a whitepowder. The purity of the crystalline final product was analyzed by HPLCand gave a result of 98.1%. The final obtained yield was 75.3 g (60%) ofa white crystalline solid. ¹H NMR (300 MHz, D₂O, 25° C.): δ 3.35 (dd,12H); 3.60 (m, 4H), 3.72 (d, 4H); 4.10) (m, 8H); 4.45 (m, 2H); 6.25 (tt,2H).

Synthetic Example 4

The cationic alcohol of Example 4 in Table 1 was prepared according tothe following reaction scheme:

In the above synthetic scheme, 3.5 ml of de-ionized water was added to1.0 equivalent (1.49 g, 7.88 mmol) of TEMED-HCl in a 20 ml scintillationvial with stirbar and mixed well until a clear solution was obtained.2.2 equivalents (5.0 g, 17.35 mmol) of glycidyl2,2,3,3,4,4,5,5-octafluoropentyl ether were added. The fluoro epoxideseparated into a different layer at the bottom of the vial. The mixturewas uniformly stirred at high speed at 95° C. The cloudy mixture wasleft stirring overnight. At the end of 16 hours, a homogeneous, clearsolution was obtained. The aqueous solution was washed withdichloromethane to remove impurities. The aqueous layer was thenconcentrated under reduced pressure using a rotovap. The material wasre-dissolved 2 to 3 times in absolute acetone and concentrated againusing a rotovap to remove any remaining water. A sticky material wasobtained. The mixture was purified by repeated precipitation (3 to 5times) from acetone with hexane. The solution was decanted off and theprecipitate dried under vacuum overnight yielding approximately 3.7 g(80%) of a white/beige powder. ¹H NMR (300 MHz, D₂O, 25° C.): δ 3.30(dd, 12H); 3.58 (m, 4H), 3.75 (d, 4H); 4.03 (m, 2H); 4.19 (t, 6H); 4.50(m, 2H); 6.49 (tt, 2H).

TABLE 1 Example No. Chemical Structure Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

Example 8

Example 9

 Example 10

 Example 11

 Example 12

 Example 13

 Example 14

 Example 15

Formulations

The compositions of the invention may be formulated with anycosmetically acceptable excipient and may be in the form of a spray,cream, lotion, emulsion, gel, wax, or pomade, for example. Conditioners,shampoos, sprays and creams are presently preferred formulations.

The cationic fluorinated alcohol according to the invention may bepresent in an amount up to about 99 percent by weight, in embodiments upto 75 percent by weight, in other embodiments up to 50 percent byweight, and preferably in a range of about 0.1 to about 10.0 percent byweight. Cosmetically acceptable excipients include those describedbelow, preferably provided in the general amounts set forth in theformulation examples below. However, departure from these guidelines isto be expected and is best left to the skill of the formulator.

The compositions may include other cosmetically active ingredients, toprovide cleansing, conditioning, setting, relaxing, volumizing or othercosmetically desired effects. Thus, a composition according to theinvention may be formulated as a shampoo, conditioner, mask, leave-inconditioner, and/or styling product such as a spray, cream, mousse, orgel and may be provided in combination with a dye, bleach or formulationintended to straighten or wave hair, for example, in which case anothercosmetically active ingredient would be provided in the composition inaddition to the fluorinated compound described herein, to provide thedesired effect. Additional charged ingredients (cationic, anionic, orzwitterionic) may be used to affect deposition properties.

Cosmetically acceptable excipients used in the hair care industry can bebroken down into several categories. Components from a category may beincluded or excluded from the final hair care composition depending onthe use of the final composition (e.g., hair spray, conditioner,shampoo). The categories of excipients include: (1)preservatives/antioxidants/chelating agents; (2) sunscreen agents; (3)vitamins; (4) dyes/hair coloring agents; (4) proteins/amino acids; (5)plant extracts; (6) humectants; (7) fragrances/perfumes; (8)oils/emollients/lubricants/butters; (9) penetrants; (10)thickeners/viscosity modifiers; (11) polymers/resins/hair fixatives/filmformers; (12) surfactants/detergents/emulsifiers/opacifying agents; (13)volatiles/propellants/solvents; (14) liquid vehicles/solvents; (15)salts; (16) pH adjusting agents/buffers/neutralizing agents; (17) hairconditioning agents; (18) anti-static agents/anti-frizz agents; (19)antidandruff agents; (20) hair waving/straightening agents; and (21)absorbents. Many suitable excipients falling into these categories maybe identified from standard reference texts in the cosmetics industry,and only a few illustrative examples are provided herein. Moreover, someexcipients may fall into more than one category.

Preservatives/Antioxidants/Chelating Agents

The inventive cosmetic hair care compositions may include preservatives,antioxidants, and/or chelating agents to extend the shelf-life and/orprevent the degradation of the components of the inventive composition.Exemplary preservative, antioxidants, and chelating agents useful in theinventive hair care compositions include, without limitation,ethylenediamine tetraacetic acid (EDTA) and salts thereof (e.g.,disodium EDTA), citric acid and salts thereof, methylisothiazolinone,and BHT. In embodiments, a cosmetic composition according to theinvention may include 0% to approximately 5% by weight of suchingredients.

Sunscreen Agents

The inventive cosmetic hair care compositions may include a sunscreenagent to protect the treated hair from the damaging ultraviolet rays ofthe sun. In certain embodiments, the sunscreen agent protects thetreated hair from damaging UV-A and/or UV-B rays. Exemplary sunscreenagents useful in the inventive hair care compositions include, withoutlimitation, p-aminobenzoic acid (PABA), and PABA-derivatives (e.g.,allantoin PABA, butyl PABA) which may be provided in an amount ofapproximately 0.0001% to approximately 5% by weight of the cosmeticcomposition, for example.

Vitamins

The inventive cosmetic hair care compositions may include one or morevitamins to nourish or replenish the treated hair. In embodiments, thecosmetic composition includes approximately 0.001% to approximately 5%by weight of one or more vitamins.

Dyes/Hair Coloring Agents

The inventive cosmetic hair care compositions may include a dye or otherhair coloring agent (e.g., a stain), including permanent, semi-permanentand temporary dyes. Such materials are well known in the art and may beprovided in an amount of 0.0001% to 5% by weight of the cosmeticcomposition.

Proteins/Amino Acids

The inventive cosmetic hair care compositions may include a protein,peptide, or amino acid. Such components may be added to the inventivecomposition to nourish the hair, impart a desired characteristic to hair(e.g., increase shine, increase body), or impart a desiredcharacteristic to the composition (e.g., thickening the composition).Exemplary proteins that may be added to hair care compositions include,without limitation, silkprotein, soy protein, and wheat protein. Aswould be appreciated by one of ordinary skill in the art, derivatives,mutants, fusion proteins, fragments, or combinations of any of theseproteins may also be included in the inventive cosmetic hair carecomposition. In certain embodiments, the proteins, peptides, or aminoacids may be included in the composition in a range from about 0.0001%to about 10% by weight.

Plant Extracts

The inventive cosmetic hair care compositions may include an extractfrom a plant. Plant extract may be added to the inventive composition tonourish the hair, provide a fragrance or color to the composition,impart a desired characteristic on hair, or impart a desiredcharacteristic to the composition. Extracts may be prepared from anypart of a plant, including leaves, fruit, flower, grass, vegetable, nut,root, stem, bark, and the like, according to methods known in the art. Aplant extract is typically used in an amount ranging from 0.001 to 10.0%by weight of the total composition.

Humectants

The inventive cosmetic hair care compositions may include a humectant. Ahumectant is a hydrogroscopic substance. It is typically a chemicalcompound containing hydrophilipic groups such as hydroxyl groups,amines, carboxylates, etc. Humectants are typically found in hair carecompositions to reduce static and/or to provide a moisturizing qualityto the hair care composition. The humectants attract and holds moistureon the hair. Non-limiting examples of humectants useful in the inventivehair care compositions include glycerin, glycerol, hyaluronic acid,propylene glycol. In certain embodiments, the humectant is used in thehair care composition in an amount ranging from about 1% to about 10% byweight of the composition.

Fragrances/Perfumes

The inventive cosmetic hair care compositions may optionally include afragrance or perfume. The perfume or fragrance may be used in the haircare composition in an amount ranging from 0.0001% to 10% by weight,typically in an amount ranging from 0.01% to 1% by weight.

Oils/Emollients/Lubricants/Butters

The inventive cosmetic hair care compositions may include an oil,emollient, lubricant, or butter. Oils are used in hair care compositionsto moisturize and/or nourish the hair. Generally, an oil is any fattysubstance which is liquid at room temperature (25° C.). Examplary oils,emollients, lubricants, and butters include PPG-3 benzyl ethermyristate, linear and/or branched fatty alcohols and fatty acid esters,glyceryl stearate, PEG and castor oils.

Penetrants

The inventive cosmetic hair care compositions may include a penetrant toenhance the penetration of the formulation into hair. The concentrationof the penetrant in the composition may range from 1% to 50% by weightof the composition. In certain embodiments, the concentration ofpenetrant ranges from 1% to 25% by weight.

Thickeners/Viscosity Modifiers

The inventive cosmetic hair care compositions may include a thickeningagent or a viscosity modifier. The thickening agent may be a natural orsynthetic thickening agent. In certain embodiments, the thickening agentis polymeric. In certain embodiments, the thickening agent is apolysaccharide. In certain embodiments, the thickening agent is aprotein. In certain embodiments, the thickening agent is a low meltingpoint wax. Non-limiting examples of low melting point waxes includefatty alcohols, such as stearyl alcohol, cetearyl alcohol, behenylalcohol, and the like. Non-limiting examples of synthetic polymericthickeners include polymers of acrylic acid, methacrylic acid and theirsimple esters, which may be co-polymerized with one or more organicgroups such as ethoxylated or propoxylated polymeric moieties.Non-limiting examples of such synthetic polymeric thickeners includeacrylamides copolymer PEG-150 pentaerythrityl tetrastearate, PEG-6caprylic/capric glycerides, polyacrylate-1 crosspolymer, and xanthangum. In embodiments, the concentration of thickening agent is in a rangeof 2% to 50% by weight.

Polymers/Resins/Hair Fixatives/Film Formers

Polymers, resins, hair fixatives, or film-forming agents may be used incertain of the inventive cosmetic hair care compositions at aconcentration to achieve the desired result when applied to hair. Inembodiments polyquaternium compounds, such as Polyquaternium-16, may beused as film formers. In certain embodiments, the polymer, resin, hairfixative, or film-forming agent is used in the final composition in arange from about 0.01% to about 20% by weight.

Surfactants/Detergents/Emulsifiers/Opacifiers

Surfactants, detergents, emulsifiers, and the like may be used in theinventive cosmetic hair care compositions. Such agents may work to makethe final composition homogenous or help to solubilize certainingredients of the composition. Exemplary surfactants useful in thepresent invention include sodium lauroyl methyl isethionate, sodiummethyl cocoyl taurate, sodium dodecyl sulfate, cocoamidopropyl betaine,and sodium laureth sulfate, sodium lauryl sulfate, alkyl and alkyl ethersulfates. Suitable emulsifiers include, without limitation, cetylalcohol and cetearyl alcohol. Many surfactants and emulsifiers useful inthe inventive compositionss are described in McCutcheon's Detergents AndEmulsifiers, 1984 Annual, published by Allured Publishing Corporation,which is incorporated herein by reference. An exemplary opacifier isglycol stearate. In embodiments, the inventive compositions may containa such ingredients in the range of from about 0.01% to about 20% byweight.

Propellants

Various inventive hair care compositions (such as hair sprays,particularly aerosols) contain a propellant used to expell the inventivecomposition from a pressurized container. Both liquids and gases can beused as propellants. Exemplary propellants useful in the hair carecompositions according to the invention include, without limitation,butane, dimethyl ether, and hydrofluorocarbon 152a.

Solvent

The inventive hair care compositions typically include a solvent orcombination of solvents to dissolve or solubilize the components of thecomposition. The solvent typically makes up the balance of acomposition. Exemplary organic solvents useful in the inventive haircare compositions include, without limitation denatured ethyl alcohol,isopropyl alcohol and butylene glycol. In certain embodiments, water isused as the solvent, alone or in combination with one or more organicsolvents. One or more solvents may make up from 1% to 99% by weight ofthe composition.

Salts

Various salts may also be added to the inventive hair care compositions.Salts are typically ionized and result in stoichiometrically equivalentamounts of cations and anions when dissolved in a solution. Salts aretypically soluble in water. The salt used in the inventive compositionsmay be an inorganic salt or an organic salt. Salts are typically used inhair care compositions as thickening agents, buffering agents, hairwaving agents, humectants, and/or oxidizing or reducing agents.Typically the concentration of the salt in the final composition is in arange from about 1% to about 30% by weight.

pH Adjusting Agents/Buffers/Neutralizing Agents

The inventive hair care compositions may include pH adjusting agents,buffers, neutralizing agents, and the like. Such agents may be used tolower the pH, raise the pH, or maintain the pH of the final compositionat a particular level. The concentration of the pH adjusting agent,buffer, or neutralizing agent in the final composition is generally inthe range from about 0.01% to about 10% by weight.

Hair Conditioning Agents

Hair conditioning agents may also be optionally included in theinventive cosmetic hair care compositions. Such agents may be includedin shampoos, conditioners, styling products, or hair sprays. Exemplaryconditioners include pantothenyl ethyl ether, behentrimonium chloride,behentrimonium methosulfate, cocamidopropyl betaine, hydrolyzed hairkeratin, hydrolyzed wheat protein, and hydroxypropyl guarhydroxypropyltrimonium chloride, to name a few. The concentration of thehair conditioning agent in the final composition is typically in therange from about 0.01% to about 10% by weight.

Anti-Static Agents/Anti-Frizz Agents

Anti-static agents and/or anti-frizz agents may also be optionallyincluded in the inventive cosmetic hair care compositions. Such agentsare particularly useful in hair conditioners, styling products, or hairsprays. An example of an antistatic agent is linoleamidopropylPG-dimonium chloride phosphate. Typically, anti-static or anti-frizzagent, when used, is present in a range of about 0.01% to about 5% byweight.

Antidandruff Agents

Antidandruff agents may also be included in inventive hair carecompositions. In the U.S., antidandruff agents are defined in 21 C.F.R.§358.703(b), (c), and (d) and are listed in 21 C.F.R. §358.710. Theconcentration of the antidandruff agent in the cosmetic composition maybe in the range from about 0.001% to about 10% by weight.

Hair Waving Agents/Hair Straightening Agents

The inventive hair compositions may also optionally include hair wavingagents or hair straightening agents. Such agents are used to modify hairfibers to facilitate permanent configurational changes. In certainembodiments, the agents are reducing agents which work to disruptdisulfide linkages in hair. In certain embodiments, strong alkalineagents are used as hair straightening agents. The concentration of thehair waving/hair straightening agent in the final hair care compositionmay be in a range from about 0.001% to about 20% by weight.

Absorbents

Certain hair care compositions of the present invention includeabsorbents. In certain embodiments, the inventive hair care compositionwith an absorbent is a dry shampoo. Absorbents are typically ingredientswith a large surface area which can attract other materials such aslipids. The concentration of the absorbent in the final composition mayrange from about 1% to about 50% by weight of the cosmetic composition.

The methods of treating hair according to the invention require onlythat the hair be contacted with the composition, and the methods may bethe same as, or combined with, conventional methods for hair treatment.For example, and not by way of limitation, the method may include a stepof shampooing the hair followed by rinsing, a step of conditioning thehair followed by rinsing, a step of spraying the hair to provide set orother cosmetic advantage, not immediately followed by rinsing, or a stepof working a lotion into the hair, not immediately followed by rinsing.In embodiments, a method according to the invention involves a treatmentof the hair after a bleaching or dying operation. Other possibilitiesfor providing improved feel and hydrophobicity to hair, in differenthair care contexts, would be apparent to one of ordinary skill in theart.

The compositions are often aqueous. Water, or a mixture of water and alower alcohol, may be present in an amount of about 50 percent by weightto about 99 percent by weight.

Non-limiting examples of compositions ranges for different formulationsof the cationic fluorinated alcohol include the following:

Formulation Example 1

An exemplary styling spray according to the invention contains:

Ingredients % w/w Water q.s. Cationic Fluorinated Alcohol  0.1-10.00Preservative 0.05-1.25

Formulation Example 2

An exemplary simple shampoo according to the invention contains:

Ingredients % w/w Water q.s. Cationic Fluorinated Alcohol  0.1-10.00Sodium Lauroyl Methyl Isethionate 5.00-17.00 Sodium Methyl CocoylTaurate 5.00-17.00 Cocamidopropyl Betaine 5.00-17.00Ethylenediaminetetraacetic acid 0.1-0.4  PEG-150 PentaerythritylTetrastearate 0.1-2.00 PEG-6 Caprylic/Capric Glycerides 0.1-2.00Preservative 0.05-1.25 

Formulation Example 3

An exemplary simple conditioner according to the invention includes:

Ingredients % w/w Water q.s. Cationic Fluorinated Alcohol  0.1-10.00Cetearyl Alcohol 4.00-8.00 Behentrimonium Chloride 0.50-3.00Preservative 0.05-1.25

Formulation Example 4

An exemplary leave-in conditioner according to the invention includes:

Ingredients % w/w Water Polyacrylate-1 Crosspolymer 0-1% Emulsifying WaxNF 0-8% Glycol Stearate 0-5% Behentrimonium Methosulfate 0.5-5%  CetylAlcohol 0.2-5%  Butylene Glycol 0-1% PPG-3 Benzyl Ether Myristate 0-5%Panthenol 0-2% Glycerin 0-10%  Fragrance 0.1-1%  Phenoxyethanol0.3-0.5%    Methylisothiazolinone 0.05-0.1%   Lauryl Methyl Gluceth-100-5% Hydroxypropyldimonium Chloride Cationic Fluorinated Alcohol 0.1-5% 

Formulation Example 5

Another exemplary hair treatment spray according to the inventionincludes:

Ingredients %w/w Water Behentrimonium Methosulfate 0.5-1% Cetyl Alcohol0.2-0.5%  Butylene Glycol 0-0.5% PPG-3 Benzyl Ether Myristate  0-1%Lauryl Methyl Gluceth-10 0-0.5% Hydroxypropyldimonium ChloridePantothenyl Ethyl Ether  0-1% Linoleamidopropyl PG-dimonium ChloridePhosphate 0-0.5% Polyquaternium-16 0-0.5% Fragrance  0-1% Phenoxyethanol0.3-0.5%  Methylisothiazolinone 0.05-0.1%   Cationic Fluorinated Alcohol0.1-5%Performance Criteria

Hair treated with the composition performs well in standard “feel tests”when tested against certain prior art compositions. Repeatedapplications with the compositions according to the invention yieldincreased deposition of the active compound on hair.

Feel Test

In order to test the performance of a shampoo and conditioner preparedaccording to the invention against a prior art formulation, shampoo andconditioner compositions were prepared based on Formulation Examples 2and 3 above, using 2 wt % the compound of Example 2 above. This wastested against a leading commercial “damage repair” shampoo andconditioner: Plain bleached hair was used as an internal control.

To prepare the samples for the feel test, 6 g of virgin medium brownhair was bleached using: 30 g of ultra concentrated bleach powder(Clairol) well mixed with 70 ml of 40V Hydrogen peroxide solution (PureWhite, Clairol). The paste was manually worked into the hair fibers tosaturate the samples. The samples were sandwiched in aluminum sheets andplaced in an oven at 50° C. for 30 minutes for “level 1” damage. A 7.5%solution of sodium lauryl sulfate solution was used to shampoo thetresses and they were blow-dried for a few minutes and allowed toair-dry at room temperature for at least 2 hours. For “level 2” damage,the tress was bleached a second time following the same procedure, butfor only 20 minutes and at room temperature. For “level 3” damage, thelevel 1 damaged tress is bleached using the same amounts as before, butfor 20 minutes at 50° C. in an oven.

The protocol for shampooing and conditioning was as follows: The hairwas wetted for 10 seconds. 350 mg of shampoo was applied to 1.5 g ofhair. The hair was lathered for 30 seconds and rinsed for another 30seconds. The tress was blotted between paper towels and 350 mg of theconditioner was applied to the hair. The conditioner was worked throughthe hair for 30 seconds, followed by rinsing for another 30 seconds. Thetress was then blotted dry and blow-dried straight if necessary.

For each feel test, the respective virgin hair is used as the control.The first tress is evaluated with respect to the control and assessed inattributes such as softness, smoothness, and oil residue/grease. Eachattribute is rated with respect to the control as shown in Table 2.Between the evaluation of each tress, hands are washed and dried.

TABLE 2 Positive Rating for Attribute Negative Rating for Attribute 0Feels like virgin −1 Slightly worse than hair the control +1 Slightlybetter, −2 Noticeably not as Barely noticeable good as the control +2Noticeably better −3 Undesirable +3 Exceptionally better

As shown in FIG. 1 through FIG. 6, the scores for each attribute at eachlevel of damage were plotted, as were the scores for combinedattributes. The compositions according to the invention showed a betterfeel performance at every level of damage compared to the prior art. Asshown in FIG. 7, the compositions according to the invention show animprovement in feel scores as the level of damage increases.

Contact Angle Measurements

As described previously, improving upon benefits such as hydrophobicity,shine and tactile properties leads to the perception of healthier, moreconditioned hair. Contact angle measurement has proven to be a viablemethod to measure the degree of hydrophobicity of hair. In principle, itmeasures the angle at the point of contact of a liquid with a surface.If the surface is highly hydrophobic (such as virgin, untreated hair),the angle of the water droplet at the interface would be greater than90°. Likewise, a hydrophilic surface would cause the water droplet tofall flat, and the angle would be close to 0°.

Virgin black hair tresses (1.5 g each, from International HairImporters) were bleached once with a homogeneous mixture of Clairol PureWhite 20V hydrogen peroxide solution (45 ml) and Clairol bleach powderUltra Concentrate BW2000 (6.75 g) for 10 min at 50° C. The tresses wereshampooed with a 7.5% Sodium Lauryl Sulfate solution twice and air-driedfor 24 h. A separate tress was kept aside and used without any furthertreatment in the contact angle experiment and referred to as: PlainBleached. Additionally, an untreated virgin black tress was used ashydrophobic control. The hair was shampooed twice with 7.5% SodiumLauryl Sulfate solution, air-dried for 24 h and labeled as: Virgin.

To one of the bleached tresses, 0.2 g of shampoo 51 from Table 3 wasapplied and lathered for 20 s, followed by a 20 s rinse under runningwater. The wet tress was blotted in paper towels until the water hadstopped dripping and 0.2 g of conditioner Cl from Table 4 was thenapplied to the hair. It was continuously spread through the fibers for20 s and was followed by a 20 s rinse. These 2 steps were denoted as oneshampoo-conditioner cycle. The cycle was repeated for another 19 timesto a total of 20 cycles. The tress was then labeled as: 20× Placebo.

An additional bleached tress was shampooed and conditioned 20 timesfollowing the procedure as described above using shampoo S1 andconditioner C2 (from Table 5). The tress was labeled as: 20× Active.

Contact angle measurements were performed with a Cahn DCA-312tensiometer. The tensiometer motor and balance were calibrated prior touse. ASTM Type II distilled water (BDH-1168, lot 092409A) was used asthe liquid. The water surface tension was determined with a platinumDuNuoy ring (Cat 14-812-5) to be 70.6 mN/m. The water was changed outbetween each sample.

The hair fiber diameter was measured with a precision micrometer(Mitutoyo Cat 293-761-30). Individual hair fibers were mounted in thetensiometer grip and immersed at the top speed range of 20-264micrometers/sec. The advancing and receding contact angles were measuredfor each sample, with runs performed in triplicate. The results areshown in Table 6.

TABLE 3 Shampoo formula S1 Ingredients (w/w)% Water Q.S.Polyquaternium-47 0.75 Ethylenediaminetetraacetic acid 0.3 SodiumLauroyl Methyl Isethionate 10.25 Sodium Methyl Cocoyl Taurate 13.3Cocamidopropyl Betaine 14.21 Behenyl Alcohol 0.2 Laureth-4 0.15Laureth-23 0.45 Lactamide MEA 3.0 PEG-7 Glyceryl Cocoate 3.0 Fragrance0.8 Hydrolyzed wheat protein 1.0Methylisothiazolinone/Methylchloroisothiazolinone 0.04 PEG-150Pentaerythrityl Tetrastearate (and) PEG-6 1.2 Caprylic/Capric Glycerides

TABLE 4 Conditioner formula C1 Ingredients (w/w)% Water Q.S. GuarHydroxypropyltrimonium Chloride 0.25 Citric Acid, (1% solution) 0.57Quaternium 87 2.0 Cetearyl Alcohol 6.0 Behentrimonium Chloride 2.0Hydrolyzed wheat protein 1.0Methylisothiazolinone/Methylchloroisothiazolinone 0.04 Fragrance 1.0

TABLE 5 Conditioner formula C2 Ingredients (w/w)% Water Q.S. GuarHydroxypropyltrimonium Chloride 0.25 Citric Acid, (1% solution) 0.57Quaternium 87 2.0 Cetearyl Alcohol 6.0 Behentrimonium Chloride 2.0Hydrolyzed wheat protein 1.0Methylisothiazolinone/Methylchloroisothiazolinone 0.04 Fragrance 1.0Cationic Fluorinated Alcohol 1.5 (Example 15 from Table 1)

TABLE 6 Contact Angle measurements of hair fiber after varioustreatments Average Standard Sample Advancing Deviation IdentificationAngle (°) (°) Virgin 86.8 1.5 Plain Bleached 36.3 8.4 20x Placebo 42.98.3 20x Active 71.1 2.1

The results from the contact angle measurements as described in Table 6demonstrate a significant difference in hydrophobicity between bleachedand virgin hair as the Virgin sample displays a contact angle twice thatof the Plain Bleached sample.

As observed in Table 6, the use of the placebo conditioner containingstandard cationic and conditioning compounds (20× Placebo) did notsignificantly impact the hydrophilic nature of the bleached hair.However, the addition of 1.5% cationic fluorinated alcohol Example 15 infrom Table 1 to conditioner C2 (20× Active) significantly increased thecontact angle of the bleached hair nearing that of the Virgin sample,signifying improved hydrophobicity. This data suggests that the 20×Active treated hair may behave more like virgin, undamaged hair inregards to water uptake, swelling, and friction, leading to improvedfell, look and manageability of hair.

The foregoing description of the preferred embodiments is exemplary onlyand not to be considered as limiting the invention, which is defined bythe appended claims.

What is claimed is:
 1. A compound prepared by reacting a tertiary aminewith a fluorinated epoxide, wherein the tertiary amine has the structure

wherein R^(2′), R^(3′), R^(4′), R^(5′), R^(6′) and R^(7′) are the sameor different C₁₋₆ alkyl group, which may be substituted with hydroxyl,carboxy, alkoxy or acyloxy groups, o is an integer from 1 to 20, whereinthe fluorinated epoxide has the structure

wherein R_(f) is a fluorinated organic group with a terminal CHF₂ group,wherein the fluorinated organic group is a branched or straight chainfluorinated aliphatic group, a straight or branched chain fluorinatedheteroaliphatic group, a fluorinated acyl group, a fluorinated aryl orfluorinated heteroaryl group, and the compound contains at least onequaternary ammonium moiety, at least one hydroxyl group, at least twofluorine atoms, and a terminal CHF₂ group, or a cosmetically acceptablesalt thereof, wherein the compound has the structure

wherein, X¹ is O or —(CH₂)_(m)—; R¹¹, R¹² and R¹³ are independently C₁₋₆alkyl or C₁₋₆ hydroxyalkyl; m is an integer from 1 to 20; and n is aninteger from 1 to 20; or a cosmetically acceptable salt thereof.
 2. Thecompound of claim 1, wherein the compound has the structure


3. A compound prepared by reacting a tertiary amine with a fluorinatedepoxide, wherein the tertiary amine has the structure

wherein R^(2′), R^(3′), R^(4′), R^(5′), R^(6′) and R^(7′) are the sameor different C₁₋₆ alkyl group, which may be substituted with hydroxyl,carboxy, alkoxy or acyloxy groups, o is an integer from 1 to 20, whereinthe fluorinated epoxide has the structure

wherein R_(f) is a fluorinated organic group with a terminal CHF₂ group,wherein the fluorinated organic group is a branched or straight chainfluorinated aliphatic group, a straight or branched chain fluorinatedheteroaliphatic group, a fluorinated acyl group, a fluorinated aryl orfluorinated heteroaryl group, and the compound contains at least onequaternary ammonium moiety, at least one hydroxyl group, at least twofluorine atoms, and a terminal CHF₂ group, or a cosmetically acceptablesalt thereof, wherein the compound has the structure

wherein, X¹ is —(CH₂—CH₂—O)_(p)—; R¹¹, R¹² and R¹³ are independentlyC₁₋₆ alkyl or C₁₋₆ hydroxyalkyl; p is an integer from 1 to 10,000; and nis an integer from 1 to 20; or a cosmetically acceptable salt thereof.4. A compound prepared by reacting a tertiary amine with a fluorinatedepoxide, wherein the tertiary amine is a diamine with the structure

wherein R^(4′), R^(5′), R^(6′) and R^(7′) are the same or different C₁₋₆alkyl group, which may be substituted with hydroxyl, carboxy, alkoxy oracyloxy groups, o is an integer from 1 to 20, wherein the fluorinatedepoxide has the structure

wherein R_(f) is a fluorinated organic group with a terminal CHF₂ group,wherein the fluorinated organic group is a branched or straight chainfluorinated aliphatic group, a straight or branched chain fluorinatedheteroaliphatic group, a fluorinated acyl group, a fluorinated aryl orfluorinated heteroaryl group, and the compound contains at least onequaternary ammonium moiety, at least one hydroxyl group, at least twofluorine atoms, and a terminal CHF₂ group, or a cosmetically acceptablesalt thereof, wherein the compound has the structure

wherein, A′ and A″ are independently CH₂, CHF or CF₂; X′ and X″ areindependently O, CF₂, or —(CH₂)_(m)—; R⁵ and R¹⁰ are the same ordifferent organic groups, each substituted with at least two fluorineatoms; R⁶ and R⁹ are independently substituted or unsubstituted C₁₋₆alkyl, and R⁶ and R⁹ may join to form a ring; R⁷ and R⁸ areindependently substituted or unsubstituted C₁₋₆ alkyl, and R⁷ and R⁸ mayjoin to form a ring; n is an integer from 1 to 6; and m is an integerfrom 1 to 20, or a cosmetically acceptable salt thereof.
 5. The compoundof claim 4, wherein the compound has the structure